CN113304781B - Heterogeneous catalytic oxidation catalyst, preparation method and method for treating phenol-containing wastewater - Google Patents
Heterogeneous catalytic oxidation catalyst, preparation method and method for treating phenol-containing wastewater Download PDFInfo
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- CN113304781B CN113304781B CN202110472167.8A CN202110472167A CN113304781B CN 113304781 B CN113304781 B CN 113304781B CN 202110472167 A CN202110472167 A CN 202110472167A CN 113304781 B CN113304781 B CN 113304781B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 62
- 239000002351 wastewater Substances 0.000 title claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 58
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 150000007524 organic acids Chemical group 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 20
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000002912 waste gas Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004880 explosion Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229960001484 edetic acid Drugs 0.000 description 9
- -1 rare earth lanthanide Chemical class 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 3
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- KZBOXYKTSUUBTO-UHFFFAOYSA-N 2-methyl-1,4-dinitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1[N+]([O-])=O KZBOXYKTSUUBTO-UHFFFAOYSA-N 0.000 description 2
- SYDNSSSQVSOXTN-UHFFFAOYSA-N 2-nitro-p-cresol Chemical compound CC1=CC=C(O)C([N+]([O-])=O)=C1 SYDNSSSQVSOXTN-UHFFFAOYSA-N 0.000 description 2
- INYDMNPNDHRJQJ-UHFFFAOYSA-N 3,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1 INYDMNPNDHRJQJ-UHFFFAOYSA-N 0.000 description 2
- PIIZYNQECPTVEO-UHFFFAOYSA-N 4-nitro-m-cresol Chemical compound CC1=CC(O)=CC=C1[N+]([O-])=O PIIZYNQECPTVEO-UHFFFAOYSA-N 0.000 description 2
- WGBAJZCLSILROV-UHFFFAOYSA-N 5-methyl-5-nitrocyclohexa-1,3-dien-1-ol Chemical compound [N+](=O)([O-])C1(CC(=CC=C1)O)C WGBAJZCLSILROV-UHFFFAOYSA-N 0.000 description 2
- JVICQVYDINUWRP-UHFFFAOYSA-N CC1(C)C(O)=CC([N+]([O-])=O)=CC1 Chemical compound CC1(C)C(O)=CC([N+]([O-])=O)=CC1 JVICQVYDINUWRP-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- SQHTUWVCXAANLL-UHFFFAOYSA-N azane;2,3-dinitrophenol Chemical compound [NH4+].[O-]C1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O SQHTUWVCXAANLL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a heterogeneous catalytic oxidation catalyst, a preparation method and a method for treating phenolic wastewater, wherein the catalyst comprises the following components: the carrier is nano iron modified semicoke, and the active component is organic acid complex metal copper and/or rare earth metal cerium. The catalyst prepared by the invention has the characteristics of high catalytic efficiency, small metal loss, good stability and the like, is favorable for converting various phenols in the phenol-containing wastewater into micromolecular acid, improves the biochemical property of the wastewater, simultaneously removes ammonia nitrogen in the wastewater and reduces the wastewater treatment cost.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to a heterogeneous catalytic oxidation catalyst, a preparation method thereof, and a method for carrying out dephenolization and ammonia removal treatment on DNT wastewater by using the heterogeneous catalytic oxidation catalyst.
Background
The TDI (toluene diisocynate) device comprises processes of preparing TDA (toluene diamine) by hydrogenating DNT (dinitrotoluene), preparing TDI by phosgenating TDA and the like, waste water generated in the DNT process mainly comprises DNT, dinitrocresol, ammonia nitrogen and the like, and DNT waste water treatment technology relates to a few schemes, and mainly comprises incineration or pre-treatment and regeneration treatment technology at present. Conventional pretreatment techniques, such as conventional Fenton treatment, produce large quantities of iron sludge, which is generally hazardous solid waste and costly to dispose. By utilizing the heterogeneous catalytic oxidation technology without solid waste, the treatment cost can be greatly reduced, the inhibitory substances DNT and dinitrocresol are removed, the ammonia nitrogen concentration is reduced, and the biochemical receiving condition is met. The technical difficulty of the pretreatment process lies in how to efficiently remove dinitro phenol ammonium and DNT, and simultaneously, the generated waste gas is used for blowing off to further remove ammonia nitrogen in the waste water, so that the biochemical property of the waste water is improved, and the key points of the pretreatment process lie in the removal rate and the stability of the heterogeneous catalytic oxidation catalyst on the COD of the waste water.
Disclosure of Invention
The invention aims to provide a heterogeneous catalytic oxidation catalyst, which can greatly improve the removal rate of dinitrocresol and DNT, has small metal loss amount and good stability, and does not generate secondary pollution.
It is another object of the present invention to provide a method for preparing such a heterogeneous catalytic oxidation catalyst.
The invention also aims to provide a dephenolization and ammonia removal treatment process for the phenolic wastewater, which is simple and feasible in treatment method and high in treatment efficiency.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a heterogeneous catalytic oxidation catalyst, the catalyst comprising a support which is modified semicoke (SCe) and an active component supported on the support, the active component being an organic acid complex metal copper and/or a rare earth lanthanide metal, preferably the active component being an organic acid complex metal copper and/or a rare earth cerium.
In a particular embodiment, the organic acid is selected from at least any one of ethylenediaminetetraacetic acid (EDTA), hydroxyethylidene diphosphonic acid (HEDP), Citric Acid (CA), or Tartaric Acid (TA).
In a specific embodiment, the content of the metallic copper is 0.1 to 1.0 wt%, preferably 0.5 wt% based on the total weight of the carrier; the content of the rare earth metal cerium is 0-1.0 wt%, and preferably 0.5 wt%.
In a specific embodiment, the modified semicoke (SCe) is a nano zero-valent iron modified semicoke; preferably, the modification method comprises: (1) pretreating SCe samples with concentrated sulfuric acid and concentrated nitric acid, mixing SCe and nano zero-valent iron at a mass ratio of 20-100:1, preferably 20-50:1, adding deionized water to prepare a 1-10% mixed solution, and performing ultrasonic treatment at 30-60 ℃ for 30-120 min; then placing the mixture in a constant-temperature drying oven to dry at 75-85 ℃ to obtain slurry, and taking the slurry for pelleting; placing the particles in a titanium alloy oxidation reaction tube, introducing steam for 5-20mL/min, controlling the reaction temperature at 120-280 ℃, preferably 180-200 ℃, reacting for 5-12h, preferably 6-8h, cooling to room temperature, washing with deionized water for 3-5 times, washing with anhydrous ethanol for 3-5 times, drying in a constant temperature drying box at 105 ℃ for 3-5 timesObtaining a modified semicoke carrier after 2-3 h; more preferably, the average particle size of the nano zero-valent iron is 10-50nm, the purity is more than 99.9%, and the specific surface area is more than 20m 2 The spherical crystal form is further preferable.
In one embodiment, the preparation method of the organic acid complex metal copper and rare earth metal cerium comprises the following steps: mixing cerium chloride and copper chloride according to a mass ratio of 0-1, and mixing an organic acid and a metal mixture according to a mass ratio of 5: (0.1-2), adding deionized water to prepare a mixed solution, for example, 0.2g/mL, uniformly stirring, heating and ultrasonically treating under a nitrogen atmosphere, and reacting at the temperature of 30-80 ℃, preferably 60-75 ℃ for 0.5-5 h, preferably 3-4 h to obtain the organic acid complex metal copper and/or rare earth metal cerium.
In another aspect of the present invention, the preparation method of the heterogeneous catalytic oxidation catalyst comprises the following steps:
adding a modified semicoke carrier into organic acid complex metal copper and/or rare earth metal cerium for impregnation in a nitrogen atmosphere, wherein the impregnation mass ratio is 1: (0.1-5), preferably 1: (1-2), soaking for 10-240 min, preferably 60-120 min; and then drying and roasting the obtained solid, preferably drying at 60-150 ℃ for 1-5 h, and roasting at 300-400 ℃ for 3-5 h to obtain the heterogeneous catalytic oxidation catalyst.
In another aspect of the present invention, the aforementioned heterogeneous catalytic oxidation catalyst is used in a method for treating phenol-containing wastewater, comprising the steps of:
1) after the pH value of the phenol-containing wastewater is adjusted to 4-6, the phenol-containing wastewater is contacted with a heterogeneous catalytic oxidation catalyst, and heterogeneous catalytic oxidation reaction is carried out in the presence of hydrogen peroxide;
2) introducing inert gas to dilute the oxygen-containing waste gas generated by the reaction in the step 1) so that the oxygen concentration is below the explosion limit;
3) adjusting the pH value of the treated wastewater to 9-12 to form free ammonia, and blowing off the reaction produced water by the waste gas diluted in the step 2) to volatilize and remove ammonia nitrogen.
In one embodiment, the heterogeneous catalytic oxidation reaction has a reaction temperature of 60 deg.CThe temperature is about 90 ℃, preferably about 60-80 ℃; the reaction pressure is 0-1.0MPa, preferably 0.5-0.8 MPa; the liquid hourly space velocity is 0.2-5h -1 Preferably 0.5-2h -1 。
In a specific embodiment, the molar ratio of the COD in the hydrogen peroxide and the phenolic wastewater is 0.1-2, preferably 0.5-1.0.
In a specific embodiment, the phenol-containing wastewater is wastewater containing Dinitrotoluene (DNT), nitrophenol and ammonia nitrogen; preferably, the COD of the DNT wastewater is 2800-3600 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the heterogeneous catalytic oxidation catalyst, semicoke (SCe) is used as a carrier, and the multi-valence state iron modified carrier is obtained by modifying nano zero-valent iron, so that the multi-valence state iron modified carrier becomes a resource recycling carrier with large specific surface area, strong adsorption performance and large loading capacity, and the contact efficiency with hydrogen peroxide and organic matters is high. The loaded organic acid complex bimetallic copper chloride and cerium chloride can avoid metal loss in the modified semicoke (SCe), and hydrogen peroxide is quickly converted into hydroxyl free radicals, so that organic matters are catalytically decomposed, and the catalyst is high in efficiency, low in cost and wide in industrial application prospect.
(2) According to the method for treating the phenol-containing wastewater by using the heterogeneous catalytic oxidation catalyst, the hydrogen peroxide is continuously and stably catalyzed to generate the hydroxyl free radical under the action of the catalyst, the hydroxyl free radical has strong oxidizing property, organic matters can be oxidized into micromolecular organic acid and alcohol, the carbon dioxide and water are further mineralized, the catalytic efficiency is high, the method is simple and easy to operate, the operation cost is low, and no secondary pollution is caused.
(3) The heterogeneous catalytic oxidation catalyst is not only suitable for the dephenolization and ammonia removal treatment of various phenolic wastewater, but also suitable for the treatment of other wastewater difficult to be biochemically treated and ammonia-containing wastewater.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
The heterogeneous catalytic oxidation catalyst of the invention has a carrier of modified semicoke (SCe), wherein the modified semicoke carrier is loaded with organic acid complexed metallic copper and/or rare earth metal cerium, preferably, the organic acid complexed metallic copper is loaded, or the organic acid complexed metallic copper and the rare earth metal cerium are loaded.
The semicoke (SCe) is a solid product obtained by low-temperature (500-700 ℃) dry distillation of peat, lignite or high-volatile bituminous coal and the like, has a porous structure of a catalyst carrier and is low in cost. Commercial semicoke products can be purchased, and the performance indexes of the commercial semicoke products are not particularly limited, such as the hundred million coal semicoke 65996-77-2.
The heterogeneous catalytic oxidation catalyst of the invention modifies the semicoke carrier, preferably by nanometer zero-valent iron, to obtain modified semicoke. The invention adopts nano zero-valent iron to modify semicoke (SCe), the zero-valent nano iron is selected from the raw materials of the processed finished products, the preferred average grain diameter is 10-50nm, the purity is more than 99.9 percent, and the specific surface area is 20-100m 2 In terms of/g, spheroidal forms are preferred. After the semicoke (SCe) and the nano zero-valent iron are fully mixed, the nano zero-valent iron and the semicoke (SCe) are mutually adsorbed, after moisture is volatilized, the slurry is compressed into particles, under the action of water vapor and temperature, the nano zero-valent iron is partially oxidized into oxides of ferrous iron and ferric iron, and the oxides are wrapped and attached on the surface of the multi-walled carbon nano tube porous oxide of the semicoke to form the multi-valence state iron modified carrier.
Under the conditions of different nano zero-valent iron adding amount, water vapor amount and temperature, Fe/Fe 2+ /Fe 3+ The proportion is different, and different parameters can be selected for customization according to different required carrier properties, including magnetism, strength, pore diameter and the like. The specific modification method is not particularly limited, and examples thereof include: (1) grinding SCe sample, for example, 20-50 mesh, soaking with concentrated sulfuric acid (mass fraction 98%) and concentrated nitric acid (mass fraction 68%) at a volume ratio of SCe to 1:1:1, stirring for 2h, centrifuging to remove acid solution, washing with water to neutrality, mixing SCe and nanometer zero-valent iron at a mass ratio of 20-100:1, preferably 20-50:1, adding deionized water to prepare 1-10% of mixed solution, and carrying out ultrasonic treatment at 30-60 ℃ for 30-120 min; then placing the mixture in a constant-temperature drying oven to dry at 75-85 ℃ to obtain slurry, and taking the slurry for pelleting. (2) Placing the particles obtained by pressing in the step (1) in a titanium alloy oxidation reaction tube, introducing 5-20mL/min of water vapor, controlling the reaction temperature at 120-280 ℃, preferably 180-200 ℃, reacting for 5-12h, preferably 6-8h, cooling to room temperature, washing for 3-5 times with deionized water, washing for 3-5 times with absolute ethyl alcohol, and drying for 2-3h at 105 ℃ in a constant temperature drying box to obtain the nano zero-valent iron modified semi-coke carrier.
Fe is generally considered to be FeO → Fe 3 O 4 →Fe 2 O 3 And (4) oxidizing in the process. FeO has an extremely unstable state and forms Fe under acidic conditions 2+ When heated in air, the iron oxide will be oxidized into Fe 3 O 4 。Fe 2 O 3 Has stronger catalytic performance, can convert an oxidant into hydroxyl free radicals, and has stable property. Fe 3 O 4 (Fe 2 O 3 FeO) has magnetic properties, with two valencies (+3, + 2). In the nano zero-valent iron modified porous semi-coke carrier, Fe → Fe is formed 2+ →Fe 3+ The conversion process of (2) continuously provides active metal continuously, and ensures the catalytic reaction efficiency.
The organic acid is one of ethylenediamine tetraacetic acid (EDTA), hydroxyethylidene diphosphonic acid (HEDP), Citric Acid (CA) and Tartaric Acid (TA), and preferably citric acid. The metal copper and the rare earth metal cerium are preferably added in equal mass, and the total mass of the carrier of the heterogeneous catalytic oxidation catalyst is calculated, wherein the content of the metal copper is 0.1-1.0 wt%, and is preferably 0.5 wt%; the content of the rare earth metal cerium is 0-1.0 wt%, preferably 0.5 wt%.
The preparation method of the organic acid complex metal copper and the rare earth metal cerium comprises the following steps: mixing cerium chloride and copper chloride according to a mass ratio of 0-1, preferably mixing cerium chloride and copper chloride in the same mass ratio to obtain a metal mixture, and mixing an organic acid and the metal mixture according to the mass ratio of 5: (0.1-2), preparing a mixed solution of 0.2g/mL by using deionized water, uniformly stirring, heating and ultrasonically treating the mixed solution in a nitrogen atmosphere, and reacting the mixed solution for 0.5-5 hours, preferably 3-4 hours at the temperature of 30-80 ℃, preferably 60-75 ℃ to obtain the organic acid complex metal copper and/or rare earth metal cerium.
It is understood that when the mass ratio of cerium chloride to copper chloride is 0, i.e., only copper chloride is added, the organic acid and copper chloride are mixed in a mass ratio of 5: (0.1-2), adding deionized water to prepare a mixed solution of 0.2g/mL, uniformly stirring, heating and ultrasonically treating under a nitrogen atmosphere, and reacting at the temperature of 30-80 ℃, preferably 60-75 ℃ for 0.5-5 h, preferably 3-4 h to obtain the organic acid complex metal copper.
In the active components, copper and cerium are main active metals, the preferable bimetallic complexation can improve the generation rate of hydroxyl free radicals and improve the removal effect of organic matters, and on the other hand, the active metal loss can be reduced through organic acid complexation, so that the service life and the stability of the catalyst are improved. The organic acid complexing agent generally contains amino groups, carboxylic acid groups or phosphonic acid groups and other coordination groups, so that a water-soluble stable complex is easily formed with heavy metal cations, and the heavy metal migration and conversion capacity is remarkably enhanced. In the present invention, the metal copper may also be a copper-based metal of group i B, such as gold and silver, but in the actual production process, copper is usually used for reasons of cost, and it should be understood by those skilled in the art that the use of gold or silver instead of copper should be regarded as an equivalent scheme of the present invention and should also be within the protection scope of the present invention. Similarly, the rare earth lanthanide metal can be, but is not limited to, lanthanum, praseodymium, neodymium, samarium, europium, etc. in addition to the commonly used cerium.
Meanwhile, the porous semicoke is used as a carrier, the complex is adsorbed by utilizing the pore channel principle, the organic acid complex metal copper and the rare earth metal cerium exist in the pore channel more firmly through the actions of static electricity, chelation and the like between the heavy metal and the organic acid, and meanwhile, hydrogen peroxide and the surface heavy metal generate more active electronic transition behavior. Because Fe (III) can form an iron carboxyl complex, and the iron carboxyl complex can generate a ligand-metal electron transfer process (LMCT) under the condition of hydrogen peroxide so as to destroy the structure of an organic matter, the method has great advantage in the aspect of exciting the removal of the organic matter in the wastewater. Therefore, the semicoke is used as a carrier, Fe (2+) and Fe (3+) are generated after modification of the nano zero-valent iron, heavy metal complexed with organic acid is immobilized by the semicoke through pore channel adsorption, and the excessive organic acid and the Fe (3+) form an iron-carboxyl complex at the same time, so that the generation of free hydroxyl by hydrogen peroxide is further promoted, the removal efficiency of characteristic pollutants in the wastewater is promoted, and particularly the wastewater generated in the DNT process is produced.
When the carrier of the catalyst is nano zero-valent iron modified semicoke (SCe), when phenolic wastewater is treated, hydroxyl free radicals are generated on organic acid complex bimetallic copper chloride and cerium chloride by hydrogen peroxide, so that phenols are converted into acid substances, and large molecules are broken into small molecules and further mineralized into carbon dioxide and water.
The heterogeneous catalytic oxidation process mainly depends on the action of a catalyst to enable hydrogen peroxide to generate hydroxyl free radicals (OH) and peroxy free radicals (O) 2 H) The active free radicals show super strong oxidation performance to organic pollutants in the wastewater through the generated synergistic effect, and chain reaction is generated to degrade the organic pollutants into micromolecular organic matters or completely mineralize the micromolecular organic matters into carbon dioxide and water, and the specific reaction process is as follows:
firstly, hydrogen peroxide catalyzes the reaction to generate the initial active free radical by the action of the catalyst:
C+H 2 O 2 →·OH+·O 2 H+C+H 2 O 2 (C represents a catalyst)
BH+·O 2 H→·OB+H 2 O (BH organic matter)
BH+·OH→·B+H 2 O
This is followed by the generation of a large number of reactive free radicals, which interact with the molecule:
·OB+H 2 O 2 →·OOB+H 2 O
·B+H 2 O 2 →·OB+H 2 O
BH+·OB→·B+BOH
BH+·OOB→BOOH+B
as can be seen from the reaction process, the main oxidation process in the heterogeneous catalytic oxidation reaction is to complete the degradation of organic matters by active free radicals with strong oxidizing property. Compared with the conventional Fenton method, the heterogeneous catalytic oxidation technology of the invention uses the fixed bed catalyst, thereby not only avoiding the generation of sludge, but also improving the conditions required by the reaction, and being an efficient wastewater treatment technology.
The preparation method of the heterogeneous catalytic oxidation catalyst comprises the following steps: adding a carrier into organic acid complex metal copper chloride or organic acid complex bimetallic copper chloride + cerium chloride for impregnation in a nitrogen atmosphere, wherein the impregnation mass ratio of the organic acid complex metal copper chloride or the organic acid complex bimetallic copper chloride + cerium chloride to the modified semicoke carrier is 1: (0.1-5), preferably 1: (1-2), soaking for 10-240 min, preferably 60-120 min; and then drying and roasting the obtained solid, preferably drying at 60-150 ℃ for 1-5 h, and roasting at 300-400 ℃ for 3-5 h to obtain the heterogeneous catalytic oxidation catalyst.
In another aspect, the heterogeneous catalytic oxidation catalyst is used in a process for removing phenol and ammonia from phenol-containing wastewater, and comprises the following steps:
(1) after the pH value of the phenol-containing wastewater is adjusted to 4-6, the phenol-containing wastewater is introduced into a heterogeneous catalytic oxidation reactor, is contacted with a heterogeneous catalytic oxidation catalyst, and is subjected to heterogeneous catalytic oxidation reaction in the presence of hydrogen peroxide, wherein the hydrogen peroxide is catalyzed to generate hydroxyl radicals under the action of the heterogeneous catalytic oxidation catalyst, and the hydroxyl radicals are subjected to oxidation reaction on dinitrocresol and nitrophenol;
(2) in the reaction process of the step (1), dinitro cresol ammonium in the wastewater is oxidized into a small molecular substance or carbon dioxide and water, meanwhile, part of hydrogen peroxide is decomposed into oxygen, and inert gas is introduced to dilute the generated waste gas containing oxygen, for example, nitrogen is used to dilute the waste gas, so that the concentration of the waste gas is below the explosion limit (2%);
(3) adjusting the pH value of the treated wastewater to 9-12 to form free ammonia from ammonia nitrogen in the wastewater under an alkaline condition, blowing off the reaction produced water by the waste gas diluted in the step 2), and volatilizing and removing the ammonia nitrogen formed by the ammonia nitrogen at the temperature of 60-90 ℃. Preferably, the volatilized ammonia gas enters the complementary collection tower to form ammonia water for ammonia washing of the DNT wastewater.
Wherein the phenol-containing wastewater is wastewater containing Dinitrotoluene (DNT), nitrophenol and ammonia nitrogen; for example, phenolic wastewater comprises: DNT wastewater COD 2800-3600mg/L, DNT comprises: 2,6-DNT27-80mg/L, 2,5-DNT 0-10mg/L, 2,3-DNT0.4-3.6mg/L, 2,4-DNT 30-130mg/L, 3,4-DNT 0.6-7mg/L, TNT 0-3.5mg/L, nitrophenol comprises: 7-70mg/L of 4-nitro-m-cresol, 0.2-42mg/L of 3-nitro-m-cresol, 0.5-6mg/L of 2-methyl-5-nitro-cresol, 0.6-2.2mg/L of 2, 6-nitro-p-cresol and 50-528mg/L of other phenols.
In a preferred embodiment, the temperature of the heterogeneous catalytic oxidation reaction in step (1) is 60 to 90 ℃, preferably 60 to 80 ℃; the reaction pressure is 0-1.0MPa, preferably 0.5-0.8 MPa; the liquid hourly space velocity is 0.2-5h -1 Preferably 0.5-2h -1 The mol ratio of the COD in the hydrogen peroxide and the phenol-containing wastewater is 0.1-2, preferably 0.5-1.0.
The heterogeneous catalytic oxidation reaction is carried out in a heterogeneous catalytic oxidation reactor, and can be a batch reaction or a continuous reaction. The catalyst is convenient to recycle and can be immobilized in a reactor, and the hydrogen peroxide is added into the reactor through a tee joint or a pipeline mixer at the same time or slightly in advance when the pH of the phenolic wastewater is adjusted to 4-6 and the phenolic wastewater is introduced into the reactor.
According to the phenol-containing wastewater treatment method, the DNT removal rate of the catalyst can reach 97% under the optimal condition, the total phenol removal rate can reach 86%, the biochemical property can be improved to 0.38 from 0.09, the ammonia nitrogen removal rate is 62%, the wastewater can directly enter a biochemical system for treatment, the removal rate is far higher than that of a traditional Fenton system by 70%, and iron-containing dangerous solid waste is not generated.
The invention is further illustrated, but not limited, by the following more specific examples.
The following examples are provided with the following main equipment types and raw material sources:
the catalytic oxidizer and its accessories are purchased from Beijing Tuochuan chemical equipment Co., Ltd;
DNT wastewater from a company plant, where COD 2800-: 27-80mg/L of 2,6-DNT, 0-10mg/L of 2,5-DNT, 0.4-3.6mg/L of 2,3-DNT, 30-130mg/L of 2,4-DNT, 0.6-7mg/L of 3,4-DNT, 0-3.5mg/L of TNT, and nitrophenol comprises: 7-70mg/L of 4-nitro-m-cresol, 0.2-42mg/L of 3-nitro-m-cresol, 0.5-6mg/L of 2-methyl-5-nitro-cresol, 0.6-2.2mg/L of 2, 6-nitro-p-cresol, and other phenols: 50-528 mg/L.
Copper chloride, cerium chloride, hydrogen peroxide, Ethylene Diamine Tetraacetic Acid (EDTA), hydroxyethylidene diphosphonic acid (HEDP), Citric Acid (CA) and Tartaric Acid (TA) are analytically pure, and concentrated sulfuric acid (mass fraction of 98%) and concentrated nitric acid (mass fraction of 68%) are purchased from national medicine group chemical reagent company Limited;
the nano zero-valent iron is from Ziboruide nanotechnology Co., Ltd;
the semicoke (SCe) is from Yiziran semicoke, has a trade name of 65996-77-2, and has a particle size of 20-50 meshes.
Preparation example 1: preparation of No. 1 catalyst (semicoke + 5% nano-iron + 5% ethylenediaminetetraacetic acid complexing CuCl) 2 /CeCl 3 )
Taking 100g of semicoke (SCe), mixing the semicoke with concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 1:1:1, mixing the materials in equal volume, stirring the mixture for 2 hours, centrifuging the mixture at 5000r/min to remove an acid solution, washing the mixture with water to be neutral, mixing the pretreated SCe and the nano zero-valent iron according to the mass ratio of 20:1, adding deionized water to prepare a mixed solution with the mass concentration of 10%, carrying out ultrasonic treatment at the temperature of 60 ℃ for 120 minutes, then placing the mixed solution in a constant-temperature drying box for drying at the temperature of 75 ℃ to obtain a slurry, taking the slurry, pressing the slurry into particles with the particle size of 5mm, and drying the particles at the temperature of 105 ℃. Placing the particles in a titanium alloy oxidation reaction tube, introducing 10mL/min of water vapor, controlling the reaction temperature at 180 ℃ for 5h, and cooling to room temperature to obtain the carrier.
Taking cerium chloride and copper chloride according to a mass ratio of 1:1, mixing ethylene diamine tetraacetic acid and the metal mixture according to a mass ratio of 5: 1, preparing a mixed solution of 0.2g/mL by using deionized water, uniformly stirring, heating and ultrasonically treating the mixed solution in a nitrogen atmosphere, and reacting the mixed solution for 3 hours at the temperature of 75 ℃ to obtain an ethylenediaminetetraacetic acid complexing copper chloride + cerium chloride solution. And (2) dissolving 5mL of the organic acid complex copper chloride + cerium chloride solution prepared in the previous step in 30% ethanol to prepare 20g of impregnation liquid, adding 20g of carrier to impregnate in a nitrogen atmosphere for 240min, drying the obtained solid at 150 ℃ for 5h, and roasting at 400 ℃ for 5h to obtain the No. 1 wet catalytic oxidation catalyst.
Preparation examples 2 to 9 catalysts 2# to 9# were prepared by replacing the carrier, the modifying substance and the addition ratio, the kind of the organic acid and the mixing ratio with the metal, the mixing ratio of the supported metal and the loading amount according to the preparation steps in preparation example 1, and the specific formulation is shown in table 1.
TABLE 1 compounding tables for catalyst preparations and comparative preparations
Example 1: DNT waste water treatment (catalyst # 1)
Adjusting the pH value of DNT wastewater to 4, adding hydrogen peroxide according to the COD of the wastewater to ensure that the molar ratio of hydrogen peroxide to COD is 1, introducing into a catalytic oxidation reaction kettle, adding a No. 1 catalyst, wherein the reaction temperature is 80 ℃, the space velocity is 2h-1, and the reaction pressure is 0.5 MPa; . Introducing nitrogen to dilute oxygen in the waste gas of the reaction tower, so that the oxygen concentration is below 4%; and adjusting the pH value of the treated wastewater to 12 to form free ammonia, and blowing off the reaction produced water by the diluted waste gas to volatilize and remove the ammonia nitrogen. The total phenol content of the effluent is 290mg/L, and the removal rate is 84%; the DNT of effluent is 1mg/L, and the removal rate is 95 percent; the biochemical property is improved to 0.38 from 0.09, the content of ammonia nitrogen is reduced to 890mg/L, and the removal rate is 60 percent.
The same batch of wastewater treatment was carried out under the reaction conditions of example 1, and the results of comparing the wastewater treatment effects of the different catalysts # 1 to # 10 are shown in Table 2.
TABLE 2 DNT wastewater treatment Performance Table for different catalysts
Different wastewater treatment process conditions were studied as follows:
example 11: DNT wastewater treatment process
Adjusting the pH value of DNT wastewater to 4, adding hydrogen peroxide according to the COD of the wastewater to ensure that the molar ratio of hydrogen peroxide to COD is 0.1, introducing into a catalytic oxidation reaction kettle, adding a No. 1 catalyst, wherein the reaction temperature is 90 ℃, the space velocity is 5h-1, and the reaction pressure is 1 MPa; introducing nitrogen to dilute oxygen in the waste gas of the reaction tower, so that the oxygen concentration is below 4%; adjusting the pH value of the treated wastewater to 10 to form free ammonia, and blowing off the reaction produced water by the diluted waste gas to volatilize and remove the ammonia nitrogen. The total phenol content of the effluent is 764mg/L, and the removal rate is 65 percent; the DNT of effluent is 4.11mg/L, and the removal rate is 79%; the biochemical property is improved to 0.24 from 0.09, the content of ammonia nitrogen is reduced to 1826mg/L, and the removal rate is 17 percent.
The reactions were carried out according to the reaction procedure of example 11, using # 1 catalyst, comparing the DNT wastewater treatment effects at different hydrogen peroxide addition amounts, different reaction temperatures, different space velocities and different reaction pressures, and the results are shown in Table 3.
TABLE 3 Effect of different wastewater treatment Process conditions
As can be seen from Table 3, the reaction has a good effect in the pH range of 4-6, and experiments also show that if the pH value is beyond the range, the equipment corrosion problem is serious due to too low pH value, and the catalyst metal loss problem is serious due to too high pH value. At a reaction temperature within 60-90 ℃, preferably 80 ℃, a temperature below 60 ℃ may result in insufficient and slow reaction; the reaction pressure is within 0.1-1MPa, preferably 0.5MPa, the reaction effect is poor when the reaction pressure is lower than the reaction pressure, and the investment of pressure-resistant equipment is high when the reaction pressure is higher than the reaction pressure. The molar ratio of the added amount of the hydrogen peroxide to the COD is 0.1-2, the hydrogen peroxide basically does not react when the molar ratio is lower than the range, the residual amount of the hydrogen peroxide is large when the molar ratio is higher than the range, the biochemical property is greatly influenced (for example, experiment No. 19), and the operation cost is high. Wherein, the 18# experiment runs continuously for 3000h, the water outlet metal ion is less than 0.1ppm, and the water production effect is stable, which shows that the metal loss of the catalyst is small, and the process stability is good. The wastewater treatment reaction and the catalyst of the invention remove characteristic pollutants in the wastewater, improve the biochemical property of the wastewater, and do not mineralize all organic matters into carbon dioxide and water at high temperature and high pressure.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (18)
1. The heterogeneous catalytic oxidation catalyst is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is modified semicoke, the active component is organic acid complex metal copper and rare earth metal cerium, and the modified semicoke is nano zero-valent iron modified semicoke;
the method for modifying the nano zero-valent iron modified semicoke comprises the following steps: taking a semicoke sample, pretreating with concentrated sulfuric acid and concentrated nitric acid, mixing the pretreated semicoke and nano zero-valent iron according to the mass ratio of 20-100:1, adding deionized water to prepare a mixed solution with the mass concentration of 1-10%, and carrying out ultrasonic treatment at 30-60 ℃ for 30-120 min; then placing the mixture in a constant-temperature drying oven to dry at 75-85 ℃ to obtain slurry, and taking the slurry for pelleting; placing the particles in a titanium alloy oxidation reaction tube, introducing 5-20mL/min of water vapor, controlling the reaction temperature at 120-280 ℃ for reaction for 5-12h, cooling to room temperature, washing with deionized water for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying in a constant-temperature drying box at 105 ℃ for 2-3h to obtain the modified semicoke carrier.
2. The heterogeneous catalytic oxidation catalyst according to claim 1, wherein the organic acid is selected from at least any one of ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, citric acid, or tartaric acid.
3. The heterogeneous catalytic oxidation catalyst of claim 1, wherein the metallic copper is present in an amount of 0.1 to 1.0 wt%, based on the total weight of the catalyst support; the content of the rare earth metal cerium is 0-1.0 wt%, and the content of the rare earth metal cerium is not 0.
4. The heterogeneous catalytic oxidation catalyst of claim 3, wherein the metallic copper is present in an amount of 0.5 wt%, based on the total weight of the catalyst support; the content of the rare earth metal cerium is 0.5 wt%.
5. The heterogeneous catalytic oxidation catalyst according to claim 1, wherein the pretreated semicoke and the nano zero-valent iron are mixed in a mass ratio of 20-50: 1; the particles are placed in a titanium alloy oxidation reaction tube, 5-20mL/min of water vapor is introduced, and the reaction temperature is controlled at 180 ℃ and 200 ℃ for reaction for 6-8 h.
6. The heterogeneous catalytic oxidation catalyst of claim 5, wherein the nano zero valent iron has an average particle size of 10 to 50nm, a purity of greater than 99.9%, and a specific surface area of greater than 20m 2 /g。
7. The heterogeneous catalytic oxidation catalyst according to claim 6, wherein the nano zero valent iron is in a spherical crystalline form.
8. The heterogeneous catalytic oxidation catalyst according to claim 1, wherein the organic acid complex metal copper and the rare earth metal cerium are prepared by a method comprising: mixing cerium chloride and copper chloride according to a mass ratio of 0-1, wherein the dosage of the cerium chloride is not 0, and mixing an organic acid and a metal mixture according to a mass ratio of 5: (0.1-2), adding deionized water to prepare a mixed solution, uniformly stirring, heating and ultrasonically treating the mixed solution in a nitrogen atmosphere, and reacting the mixed solution for 0.5-5 hours at the temperature of 30-80 ℃ to obtain the organic acid complex metal copper and the rare earth metal cerium.
9. The heterogeneous catalytic oxidation catalyst according to claim 8, wherein the reaction is carried out at a temperature of 60 to 75 ℃ for 3 to 4 hours.
10. A method for preparing a heterogeneous catalytic oxidation catalyst according to any one of claims 1 to 9, comprising the steps of:
adding a modified semicoke carrier into organic acid complex metal copper and rare earth metal cerium for impregnation in a nitrogen atmosphere, wherein the impregnation mass ratio is 1: (0.1-5), and soaking for 10-240 min; and then drying and roasting the obtained solid to obtain the heterogeneous catalytic oxidation catalyst.
11. The method according to claim 10, wherein the impregnation mass ratio is 1: (1-2) dipping for 60-120 min; drying at 60-150 ℃ for 1-5 h, and roasting at 300-400 ℃ for 3-5 h.
12. A method for treating phenol-containing waste water by using the heterogeneous catalytic oxidation catalyst according to any one of claims 1 to 9, comprising the steps of:
1) after the pH value of the phenolic wastewater is adjusted to 4-6, the phenolic wastewater is contacted with a heterogeneous catalytic oxidation catalyst, and heterogeneous catalytic oxidation reaction is carried out in the presence of hydrogen peroxide;
2) introducing inert gas to dilute the oxygen-containing waste gas generated by the reaction in the step 1) so that the oxygen concentration is below the explosion limit;
3) adjusting the pH value of the treated wastewater to 9-12 to form free ammonia, and blowing off the reaction produced water by the waste gas diluted in the step 2) to volatilize and remove ammonia nitrogen.
13. The method according to claim 12, wherein the reaction temperature of the heterogeneous catalytic oxidation reaction is 60-90 ℃; the reaction pressure is 0-1.0 MPa; the liquid hourly space velocity is 0.2-5h -1 。
14. The method according to claim 13, wherein the reaction temperature of the heterogeneous catalytic oxidation reaction is 60-80 ℃; the reaction pressure is 0.5-0.8 MPa; the liquid hourly space velocity is 0.5-2h -1 。
15. The method according to claim 12, wherein the molar ratio of the COD in the hydrogen peroxide solution and the phenolic wastewater is 0.1-2.
16. The method according to claim 15, wherein the molar ratio of the COD in the hydrogen peroxide solution and the phenolic wastewater is 0.5-1.0.
17. The method according to claim 12, wherein the phenol-containing wastewater is wastewater containing dinitrotoluene DNT, nitrophenol, ammonia nitrogen.
18. The process as claimed in claim 17, wherein the COD of the DNT wastewater is 2800 and 3600 mg/L.
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